Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
  • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
  • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/20—Recycling

Definitions

• This invention relates to a method for eluting a metal adsorbed on a chelating agent, more particularly a method for eluting a metal from a chelating agent having adsorbed the metal by using as an eluent an aqueous base solution containing a sulfide.
• Elution of a metal adsorbed on a chelating agent has heretofore been conducted generally by bringing a chelating agent having adsorbed the metal into contact with an aqueous solution of a mineral acid such as sulfuric acid, hydrochloric acid or the like.
• a mineral acid such as sulfuric acid, hydrochloric acid or the like.
• the chelating agent has a functional group having no acid resistance such as an oxime group, a phosphoric ester group or the like, it is deteriorated in capability by decomposition of the functional group. Therefore, the employment thereof is not desirable.
• an aqueous sulfide solution as an eluent is diadvantageous, for example, in that elution requires a very long time; that since metal sulfides are generally low in solubility, eluted metal is deposited as a sulfide, so that for recovering the metal, a troublesome step of dissolving and recovering the metal again is needed; and that the eluted metal is precipitated as a metal sulfide which is slightly soluble in water, therefore when a solid adsorbent is used, the metal sulfide is accumulated in the adsorbent, so that the pores are clogged therewith, resulting in deterioration of the adsorbent in capability.
• the present inventors have conducted research and have consequently found that by using as an eluent an aqueous base solution containing a specified amount of a sulfide, the metal can be recovered in a liquid state to a high concentration range with a high elution rate without essentially causing deterioration of the adsorbent, whereby this invention has been accomplished.
• the object of this invention is to provide a method for eluting a metal adsorbed on a chelating agent with an eluent, which comprises using as the eluent an aqueous solution containing a water-soluble inorganic sulfide and a basic compound at concentrations of 0.005 to 3N and 0.1N or more, respectively.
• the chelating agent which the method of this invention is intended for is not critical and said method is applicable to any chelating agent, said method is suitable particularly for chelating agents having in the molecule at least one functional group or metal salt thereof selected from the group consisting of --P(OR) 2 , --PO(OR) 2 , --PH(OR) 3 , ⁇ NOH, --N(R) 2 , --.sup. ⁇ N(R) 3 (wherein each of R's which may be the same or different represents hydrogen, is a phenyl group, an alkyl group or an alkenyl group) and their metal salts.
• Chelating agents suitably used in the above-mentioned method of this invention are those which are relatively stable under basic conditions but unstable under acidic conditions, and they include, in general, (1) chelate resin obtained by reacting a polymer of a vinyl cyanide type monomer such as acrylonitrile, ⁇ -chloroacrylonitrile, vinylidene cyanide, methacrylonitrile or the like or a copolymer of said monomer and an ethylene type unsaturated monomer copolymerizable therewith, with hydroxylamine or a derivative thereof to introduce amidoxim group into the polymer or copolymer, (2) resins obtained by polymerizing a vinyl cyanide type derivative prepared by reacting a vinyl cyanide type monomer such as acrylonitrile, ⁇ -chloroacrylonitrile, vinylidene cyanide, methacrylonitrile or the like with hydroxylamine or a hydroxylamine derivative, or by copolymerizing the vinyl cyanide type derivative with an ethylene
• the metal salts is one which is formed by ionic bond, chelate bond or complex bond between the functional group in the chelating agent and the metal, and the metal is not critical so long as these bonding strengths for the formation of the salt are lower than the bonding strength between the aforesaid functional group and a metal intended to be adsorbed and recovered.
• alkali metals and alkaline earth metals such as sodium, potassium, calcium, magnesium and the like.
• the metal may be adsorbed by any method.
• the kind of the adsorbed metal is not critical, preferable are metals soluble in eluents comprising a mixed aqueous solution of a sulfide and a basic compound, for example, gallium, germanium, indium, uranium, vanadium, gold, platinum, palladium, thallium, etc.
• aqueous solution containing a water-soluble inorganic sulfide and a basic compound in concentrations of 0.005 to 3N, preferably 0.01 to 2N, and 0.1N or more, preferably 0.2 to 25N, respectively.
• the concentration of the base is less than 0.1N, the elution rate of the metal is low, so that the elution requires a long time, and moreover the pores of the adsorbent are clogged with the metal sulfide eluted, resulting in deterioration in capability of the adsorbent. Therefore, such a base concentration is not desirable.
• the upper limit of the concentration of the basic compound is not critical, and it may be any concentration so long as the basic compound is dissolved in an eluent.
• the sulfide which is a constituent of the eluent used in the method of this invention include water-soluble inorganic sulfides such as sodium sulfide, ammonium sulfide, hydrogen sulfide, potassium sulfide, ammonium hydrogensulfide, sodium hydrogensulfide, lithium sulfide, barium sulfide, magnesium sulfide and the like.
• the basic compound which is another constituent of said eluent includes inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonia and the like, and water-soluble organic amines such as ethylenediamine, diethylenetriamine, diethylamine, triethylamine and the like. Such sulfide and basic compound are mixed and used in the form of an aqueous solution.
• the eluent is used, as described above, in the form of an aqueous solution of the constituents, it may contain organic solvents, so long as the contact treatment is not hindered.
• the amount of the eluent used is not critical and varies depending on the kind and concentration of the eluent, the kind of chelating agent, the kind and content of adsorbed metal, and the like, it can be determined by carrying out preliminary tests properly.
• the temperature at contact of the chelating agent having adsorbed a metal with the eluent is not critical, it is usually 0° to 100° C., preferably 10° to 50° C.
• the contact time is also not critical. It is, however, usually 1 minute to 24 hours.
• a method for the contact is not critical, and there is employed, for example, a method comprising passing an eluent through a column packed with a resinous chelating agent; a method comprising immersing a resinous chelating agent in an eluent, and then separating them by filtration; a method comprising adding a liquid chelating agent to an eluent, contacting and stirring them, and separating them by allowing the resulting mixture to stand; or the like.
• the metal can be recovered in the form of a metal hydroxide by carrying out treatments such as neutralization, filtration and the like, or can be recovered by subjecting the eluate as it is to treatment with a reducing agent, electrolysis and the like, though a method for recovering the metal varies depending on the kind and use of the metal.
• the chelating agent from which the metal ions have been eluted can be reused as an adsorbing and capturing agent for metal ions as it is or after, if necessary, being treated with water and/or a basic aqueous solution of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonia or the like, or an acidic aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like.
• a chelating agent having adsorbed a metal and containing a functional group which is subject to hydrolysis under acidic condition it has become possible to suppress decomposition of the easily hydrolyzable functional group at the time of elution, and it has consequently become possible to separate a metal from a chelating agent having a readily hydrolyzable functional group.
• the eluent of this invention brings about the following marked industrial effects: the elution rate is greatly increased, recovery of a metal in a liquid state to a high concentration range is made possible, and deterioration of adsorbent is greatly reduced. Therefore, its industrial significance is very large.
• a column having an inside diameter of 20 mm was packed with 100 ml of Sumichelate ®MC-60 (a chelating agent having amidoxime group, manufactured by Sumitomo Chemical Company), and sea water having a uranium concentration of 3.1 ppb was passed therethrough upward at a space velocity of 50 hr -1 for 120 hours to adsorb uranium on the chelating agent.
• Sumichelate ®MC-60 a chelating agent having amidoxime group, manufactured by Sumitomo Chemical Company
• the uranium concentration in the eluates thus obtained were as shown in Table 1.
• a column having an inside diameter of 20 mm was packed with 100 ml of Duolite ®CS-346 (a chelating agent having amidoxime group, manufactured by Diamond Shamrock Company), and sea water having a uranium concentration of 3.1 ppb was passed therethrough upward at a space velocity of 50 hr -1 for 120 hours to adsorb uranium on the chelating agent. Subsequently, an eluent having each of the compositions shown in Table 2 was passed downward at a space velocity of 10 hr -1 for 3 hours at room temperature to elute the uranium adsorbed on the chelating agent. Next, deionized water was passed upward through the column at a space velocity of 10 hr -1 for 1 hour to wash the chelating agent.
• Duolite ®CS-346 a chelating agent having amidoxime group, manufactured by Diamond Shamrock Company
• a column having an inside diameter of 10 mm was packed with 100 ml of a resinous chelating agent having ⁇ NOH group, ⁇ NH group, --NH 2 group and --NHNH 2 group prepared by reacting a copolymer of acrylonitrile and divinylbenzene with hydroxylamine sulfate and hydrazine an aqueous solution, and 3,000 ml of Bayer solution having a gallium concentration of 180 ppm and containing 18% by weight NaOH was passed therethrough for 3 hours to adsorb gallium on the chelating agent.
• a resinous chelating agent having ⁇ NOH group, ⁇ NH group, --NH 2 group and --NHNH 2 group prepared by reacting a copolymer of acrylonitrile and divinylbenzene with hydroxylamine sulfate and hydrazine an aqueous solution, and 3,000 ml of Bayer solution having a gallium concentration of 180 ppm and containing 18% by weight NaOH was
• each of the following chelating agents A to N was brought into contact with 100 ml of uranium-enriched sea water containing 100 mg/liter of uranium and having a pH of 8.3 for 3 hours, it was filtered and the residue was washed with water to obtain each chelating agent having adsorbed uranium.
• the amounts of uranium adsorbed of the chelating agents are shown in Table 3.
• a resin having an aminoalkylenephosphoric acid ester group obtained by reacting 60 parts by weight of polyacrylonitrile with 103 parts by weight of diethylenetriamine in an aqueous solvent, and further reacting the resulting aminated polyacrylonitrile with 281 parts by weight of an aqueous formaldehyde solution and 498 parts by weight of triethyl phosphite in the presence of 36% hydrochloric acid.
• a resin having a quaternary phosphonium salt group obtained by reacting 200 parts by weight of chloromethylated polystyrene with 200 parts by weight of tributylphosphine in dimethylformamide solvent.
• a resin having a quaternary phosphonium salt group obtained by reacting 200 parts by weight of chloromethylated polystyrene with 260 parts by weight of triphenylphosphine in dimethylformamide solvent.
• a resin having a phosphine group obtained by reacting 150 parts by weight of brominated polystyrene with 64 parts by weight of a 1.6 mole % solution of n-butyllithium dissolved in hexane in tetrahydrofuran solvent, reacting the resulting lithium polystyrene with 300 parts by weight of chlorodiphenylphosphine in tetrahydrofuran solvent, and then oxidizing the resulting reaction product with 371 parts by weight of 40% peracetic acid in methylene chloride solvent.
• a resin having sodium salt of phosphonic acid obtained by hydrolyzing Chelate resin B in a 20% aqueous sodium hydroxide solution.
• a resin having phosphinic acid group obtained by reacting 100 parts by weight of polystyrene with 150 parts of phosphorus trichloride in chloroform solvent, and then hydrolyzing the reaction product.
• a resin having a phosphinic acid ester group obtained by reacting 100 parts by weight of aminated polystyrene with 120 parts by weight of cresyl chloromethylphosphinate in 1,2-dichloroethane solvent.
• a resin having diethylenetriaminomethylenephosphoric acid group obtained by hydrolyzing Chelating resin A in a 2-% aqueous sodium hydroxide solution.
• a vinyldiamidodioxime-divinylbenzene-acrylic acid copolymer resin obtained by reacting a copolymer of vinylidene cyanide, divinylbenzene and methyl acrylate with hydroxylamine.
• Sumichelate ®MC-30 (a chelating agent having an iminodiacetic acid group, manufactured by Sumitomo Chemical Company).
• Duolite® ES-467 a chelating agent having aminomethylenephosphonic acid group, manufactured by Diamond Shamrock Company
• Adsorption and elution of indium were conducted in exactly the same manner as in Example 22, except that a 4 N aqueous sulfuric acid solution was used in place of the eluent used in Example 22, to find that the amount of indium adsorbed was 3,879 mg, while the amount of indium eluted was 38 mg.
• Duolite® A-161 a strongly basic ion-exchange resin having a quaternary ammonium salt, manufactured by Diamond Shamrock Company
• 98 mg of gold was adsorbed by the ion-exchange resin.
• This ion-exchange resin having adsorbed gold was added to 500 ml of a 2 N aqueous potassium hydroxide solution, and 30 liters of hydrogen sulfide gas was bubbled therethrough with stirring at room temperature over a period of 5 hours.
• this eluent consisting of H 2 S-KOH mixed aqueous solution for another 19 hours to be brought into contact therewith, 95 mg of gold was eluted.
• Adsorption and elution of gold were conducted in exactly the same manner as in Example 23, except for using a 1 N aqueous sulfuric acid solution in place of the eluent used in Example 23 and changing the stirring and contact time to 24 hours, to find that the amount of gold adsorved was 98 mg, while the amount of gold eluted was 0.9 mg.

Landscapes

• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Geochemistry & Mineralogy (AREA)
• Geology (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Environmental & Geological Engineering (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Manufacture And Refinement Of Metals (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Treatment Of Water By Ion Exchange (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=15785278

Family Applications (1)

Country Status (13)

Cited By (6)

Families Citing this family (4)

Citations (9)

Family Cites Families (2)

• 1984
  • 1984-08-03 JP JP16402184A patent/JPS6142335A/ja active Granted
• 1985
  • 1985-07-25 US US06/759,104 patent/US4786481A/en not_active Expired - Fee Related
  • 1985-07-26 IE IE188485A patent/IE58652B1/en not_active IP Right Cessation
  • 1985-07-26 CA CA000487603A patent/CA1259196A/en not_active Expired
  • 1985-07-29 IN IN554/CAL/85A patent/IN163746B/en unknown
  • 1985-07-30 EP EP85109584A patent/EP0171704B1/en not_active Expired
  • 1985-07-30 DE DE8585109584T patent/DE3570091D1/de not_active Expired
  • 1985-07-30 AU AU45589/85A patent/AU568761B2/en not_active Ceased
  • 1985-08-01 ZA ZA855823A patent/ZA855823B/xx unknown
  • 1985-08-01 YU YU1253/85A patent/YU45266B/xx unknown
  • 1985-08-02 NL NL8502181A patent/NL8502181A/nl not_active Application Discontinuation
  • 1985-08-02 GR GR851902A patent/GR851902B/el unknown
  • 1985-08-02 ES ES545852A patent/ES8605396A1/es not_active Expired

Patent Citations (10)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events